Iminoxyorganosilanes

ABSTRACT

Silanes R-Si Ya Q3 a where R is unsubstituted or halo, alkoxy or nitrile substituted hydrocarbon radical, one of Y and Q is ON CR&#39;&#39;R&#39;&#39;&#39;&#39; and the other is O(DO)nR&#39;&#39;&#39;&#39;&#39;&#39;, a a number from 0.1 to 2.9, where R&#39;&#39; is a hydrocarbon radical, R&#39;&#39;&#39;&#39; is H or C1 5 alkyl, or R&#39;&#39; and R&#39;&#39;&#39;&#39; together are divalent hydrocarbon radicals, R&#39;&#39;&#39;&#39;&#39;&#39; is C1 4 aliphatic hydrocarbon radical, D is C1 8 alkylene radical and n O, 1, 2 or 3; are prepared by reacting RSiEaQ3 a with YH where E is halogen or acyloxy. They may be used particularly as cross-linking agents for polydiorganosiloxanes having reactive terminal groups on the chain to give elastomer forming compositions which are storage stable in the absence of water and which cure to form elastomers in the presence of water at about 20* C.

United States Patent Boissieras et a1.

[451 Oct. 10, 1972 [54] IMINOXYORGANOSILANES [72] Inventors: JeanBoissieras; Louis Ceyzeriat;

Guy Poy, all of Rhone, France [73] Assignee: Rhone-Poulenc S.A., Paris,France [22] Filed: Nov. 12, 1970 [2]] Appl. No.: 89,149

[30] Foreign Application Priority Data Nov. 12, 1969 France ..6938761[52] US. Cl....260/448.8 R, 260/46.5 E, 260/465 G, 260/4482 N, 260/4482E, 260/4482 B [51] Int. Cl. ..C07f 7/18 [58] Field of Search..260/448.2N, 448.2 E, 448.8 R, 260/4482 B [5 6] References Cited UNITED STATESPATENTS 6/1965 Sweet ..260/448.2 N X 8/1969 P1ueddemann..260/448.8 R X8/1967 Culpepper ..260/448.8 R

OTHER PUBLICATIONS Noll, Chemistry and Technology of Silicones, AcademicPress, NY. (1968), pps. 81, 82, 100.

Primary ExaminerDelbert E. Gantz Assistant Examiner-P. F ShaverAttorneyStevens, Davis, Miller & Mosher 5 7] ABSTRACT Silanes R-Si Y Owhere R is unsubstituted or halo, alkoxy or nitrile substitutedhydrocarbon radical, one of Y and Q is -ON=CRR" and the other isO(DO),,R", a a number from 0.1 to 2.9, where R is a hydrocarbon radical,R" is H or C, alkyl, or R 14 Claims, N0 Drawings IMINOXYORGANOSILANESThe present invention provides new silanes containing both iminoxy andorganoxy groups bonded to the silicon atom, which can be used innumerous fields of organo-silieone chemistry.

The silanes of the present invention are those of general formula:

wherein R represents a monovalent hydrocarbon radical which may besubstituted by halogen or by an alkoxy or nitrile group, one of Y and Qrepresents a radical and the other of Y and Q represents a O (DO),,R"'radical, and a represents a positive number in the range 0.1 to 2.9inclusive; the symbols R, which may be the same or different, eachrepresent a monovalent hydrocarbon radical, the symbols R", which may bethe same or different, each represent hydrogen or an alkyl radicalcontaining one to five carbon atoms or, together with R represent adivalent hydrocarbon radical, the symbols R', which may be the same ordifferent, each represent a monovalent aliphatic hydrocarbon radicalhaving one to four carbon atoms, the symbols D, which may be the same ordifferent, each represent an alkylene radical having one to eight carbonatoms and n 0, l, 2 or 3.

More particularly, R may represent an alkyl radical having one to 12carbon atoms or an alkenyl radical having two to 12 carbon atoms, whichmay optionally be substituted by halogen or by a nitrile group; acycloalkyl or cycloalkenyl radical having three to six ring carbonatoms, which may optionally be substituted by halogen; an ethynylradical; a phenyl, alkylphenyl or phenylalkyl radical; or an alkoxyalkylradical having three to 12 carbon atoms which may optionally besubstituted by halogen or a nitrile group; R may represent an alkylradical having one to six carbon atoms or an alkenyl radical having twoto six carbon atoms, a cycloalkyl or cycloalkenyl radical having give orsix ring carbon atoms, a phenyl radical, or an alkylphenylor-phenylalkyl radical; R' may represent an alkyl radical having one tofour carbon atoms or an alkenyl radical having two to four carbon atoms;D may represent a polymethylene radical having one to four methylenegroups in the chain, which themselves may optionally be substituted by amethyl group; alternatively R and R together may form a polymethyleneradical having three to six methylene groups in the chain, whichthemselves may optionally be substituted by methyl or ethyl groups.

Specific examples of radical R which may be present in the silanes ofthe invention include the following: substituted or unsubstituted alkyland alkenyl radicals such as the methyl, ethyl, propyl, isopropyl,isobutyl,

butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. undecyl, dodecyl,vinyl, allyl, butenyl, pentenyl, deccnyl, chloromethyl, trifluoropropyl,trifluorobutyl, B- cyanoethyl and gamma-cyanopropyl radicals;cycloalkyl-and cycloalkenyl radicals having three, four, five or sixring carbon atoms, which may optionally be substituted by one to twohalogen atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopentenyl, cyclohexenyl, difluorocyclopropyl, difluorocyclobutyl anddifluorocyclohexyl radicals; alkylphenyl radicals, such as tolyl andcumenyl radicals; phenylalkyl radicals such as benzyl and phenylethylradicals; alkoxyalkyl radicals having three to 12 carbon atoms, whichmay optionally be substituted by halogen atoms or a nitrile group, suchas methoxyethyl, methoxypropyl, ethoxypropyl, ,8-

' trifluoroethoxypropyl and B-cyanoethoxypropyl radicals.

Specific examples of radicals R include alkyl and alkenyl radicals, suchas methyl, ethyl, propyl, butyl, pentyl, hexyl, allyl and butenylradicals; cycloalkyl and cycloalkenyl radicals having five or six ringcarbon atoms, such as cyclopentyl, cyclohexyl, cyclopentenyl andcyclohexenyl radicals; alkylphenyl radicals such as tolyl and xylylradicals; and phenylalkyl radicals such as benzyl radicals.

When R" represents an alkyl radical, it may be methyl, ethyl, isopropyl,propyl, butyl or pentyl.

Specific examples of radicals R include methyl, ethyl, propyl,isopropyl, isobutyl, allyl and butenyl.

Specific examples of radicals D, include methylene, ethylene, propylene,isopropylene and butylene radicals.

Specific examples of divalent polymethylene radicals having three to sixmethylene groups in the chain, which may optionally be substituted bymethyl or ethyl groups, and which are derived from the joining of tworadicals R and R" and form carbocyclic radicals with the carbon atom ofthe iminoxy group include those of formulas:

CH3 -ON C ON=C ON=O l l l l (llHa I It should be understood that thesilanes of the invention, of formula I, can be pure products ormixtures, with the degree of purity depending on the method of obtainingthese silanes and on their greater or lesser ease of purification byknown methods of organosilicon chemistry. When the symbol a has a valueof 1 or 2, the formula (I) represents a pure product; when a representsa non-integral value, the product of formula (I) is a mixture containingat least one pure product of formula I in which the value ofa is l or 2.

dichlorocyclopropyl,

Examples of specific silanes of the invention are those of formulas:

( 011201120 C2H5)3-a a, as already indicated, represents any numberranging from 0.l to 2.9.

The preparation of the silanes of formula I is effected by completereaction of a compound of general formula:

in which E represents a halogen atom or an acyloxy radical, with acompound of general formula HY.

The general reaction could thus be represented by the stoichiometricequation:

+ aEII However, radical exchange phenomena can occur on the samemolecule of the organosilicon derivative and the value of the symbol aof the product obtained can differ somewhat from the value a of thestarting product.

The symbol E may represent fluorine, chlorine or bromine atoms orradicals of formula MCOO in which M represents hydrogen, an alkylradicalwith one to four carbon atoms or an aryl radical, for example, M may bea methyl, ethyl, propyl or phenyl radical.

The process described above can be effected under conditions which varydepending on the values of E and Q in the starting material. 1. IfQ=0(DO),,R

and E halogen, about two-thirds of the stoichiometric amount of thesilane of formula II is reacted with a nitrogen-containing base in aninert diluent medium, an oxime of formula is then reacted, and finallythe resulting reaction mixture is reacted with about one-third of thestoichiometric amount of the silane of formula (ll). The resultingsilane of formula (I) is then isolated by any convenient means.

By nitrogen-containing organic base, we mean ammonia and the primaryamines.

Suitable bases include primary alkylamines or arylamines such asmethylamine, ethylamine, butylamine and aniline. However ammonia ispreferred because of its high reactivity, its low molecular weight andits ease of availability at a lower price.

The diluent which is inert towards the reagents employed is preferably achlorinated organic solvent or a hydrocarbon solvent, for example,tetrachlorethane, chlorobenzene, orthodichlorobenzene, cyclohexane,methylcyclohexane, toluene, xylene or cumene.

In a preferred method of preparing the silanes 1, twothirds of the molaramount of the halogenorganoxysilane of formula (ll) is initially used,and is diluted with an inert solvent chosen from those mentioned above,in an amount which can represent 2 to 10 times the volume of the silaneof formula (ll). A stream of anhydrous ammonia is introduced into thissolution for the requisite period of time for the reaction with theSihalogen bonds to be complete. The temperature of the reaction mediumis advantageously maintained at 5-5O C. by efficient cooling. When thereaction is complete, no more ammonium chloride forms, and the ammoniais evolved from the reactor. The oxime of the carbonyl compound, HP, isthen added to the mixture, and is used in slight excess over thetheoretical amount required to react with all the Si-halogen bonds ofthe reagent of formula (11) involved in the reaction; a molar excess of3 to 10 percent is suitable. From the time when these reagents arebrought into contact, the reaction is slightly exothermic and atemperature below 50 C. is preferably maintained by slight externalcooling. Finally, the silane (ll) not yet used, the remaining one-thirdof the total molar amount, is slowly introduced, while controlling thetemperature of the reaction mixture so that it should become establishedat below 50 C., as already indicated. It is sometimes advantageous,after adding the silane, to heat the mixture for some hours under refluxin order to complete the reaction. The mixture is thereafter treated ina usual manner: it is filtered, the residual solid is washed with aninert diluent, preferably of the same nature as that already used, thewash solvent is combined with the filtrate, and after removing thediluent and the volatile products by heating under reduced pressure, thesilane of formula (I) is obtained. In general, the

pure silanes of formula (I) in which a l or 2 can be isolated byfractional distillation; this distillation is not always necessary andit is subsequently possible, in numerous fields of application, to usethe crude mixture which frequently shows identical behavior to that ofthe pure distilled product.

The halogenosilane starting material of formula (II), in which Erepresents a halogen atom, is prepared by partial reaction of an organichydroxy compound of general formula:

I-IO(DO),,R"' (III) with a halogenosilane of formula RSiE in which Erepresents a halogen atom.

For example, the hydroxy compound of formula III is slowly added to thehalogenosilane of formula RSiE During this reaction a halogen acid EH isformed in addition to the halogenorganoxysilane of formula (II), andthis acid is removed as it is formed by carrying it away by means of aninert gas such as nitrogen or by forming a salt with a tertiary aminesuch as triethylamine or pyridine. It is sometimes advantageous to addto the reagents a diluent which is inert towards them, in order tomoderate the reaction, but its presence is not indispensable. The molarratio (III)/(IV) can vary over a wide range of values such as 0. l :1 to3.1:]. After completion of the reaction, a mixture is obtained fromwhich the silanes of formula (II), in which a has the value of l or 2,can very frequently be isolated in the pure state by fractionaldistillation; the first and last distillation runnings consistprincipally of the silanes of formula RSiE and RSI[O(DO),,R"'] However,if the distillation only separates mixtures, the latter correspond toformula II in which a can assume any value from 0.1 to 2.9. In fact, byvarying both the reaction temperature and the molar ratio III/IV, thedesired halogenorganoxysilane can be prepared as the major constituent,with a yield which can exceed 90 percent.

As halogenosilane of formula RSiE it is preferred to useorganotrichlorosilanes, such as methyltrichlorosilane,vinyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane,allyltrichlorosilane, phenyltrichlorosilane, cyclohexenyltrichlorosilaneor 2,2-dichlorocyclopropyltrichlorosilane. 2. If Q O(D),,R"

and E acyloxy, the silane of formula (II) is reacted with the oxime offormula RI HON=C the mixture is then diluted with an inert solvent, anitrogen-containing base is added to complete the reaction, and thedesired silane of formula (I) is isolated.

A preferred way of carrying out this process is to introduce the oximeof formula into the reactor, containing the silane of formula (II), in asufficient molar amount to neutralize all the acyloxy radicals present;in general, a molar excess of about 5 to percent of this oxime is used.The reaction is slightly exothermic, and the temperature easily settlesdown to below 50 C. To complete the reaction, that is to say, to reactthe acyloxy radicals still bonded to the silicon, the reaction mixtureis diluted with an inert diluent at the rate of 0.5 to 5 times thevolume of the reagents, and ammonia is immediately introduced for therequisite time for the reaction with the mixture to be complete. Thereaction with ammonia is rather vigorous and the temperature can be keptwithin the range of -70 C. by cooling from outside the reactor; whenammonia is evolved from the reactor, the introduction of ammonia isstopped and the silane of formula (I) is isolated from the reactionmixture in the way already indicated in the variant of the process inwhich E represents a halogen atom.

The starting silane Ea RS1 of formula (II), in which E represents anacyloxy radical can be obtained by partial reaction of an organichydroxylic compound of general formula:

HO(DO),,R' m with a triacyloxysilane of general formula RSiE (IV) inwhich E represents an acyloxy radical.

In a preferred method for the preparation of this intermediate offormula (II) a calculated molar amount of the hydroxy compound offormula III which would theoretically form the silane of formula (11)having the desired value a is added to an organotriacyloxysilane offormula (IV). The reaction can take place in an inert diluent medium; ifthe triacyloxysilane has a rather low melting point, the process ispreferably carried out without a diluent by simply introducing thehydroxy compound into the molten silane, and the temperature changesgradually, ranging from the melting point of the triacyloxysilane toambient temperature (about 20 C.). The organic acid formed and thevolatile products are thereafter removed by distillation under reducedpressure, avoiding, if possible, exceeding a temperature of l50 C. inthe material. A mixture of silanes of formula (II) is thus obtainedwhich consists predominantly of the desired silane, which can beisolated pure by known means of organic chemistry.

The starting organotriacyloxysilane may be a methyltriacetoxysilane, avinyltriacetoxysilane or a phenyltriacetoxysilane. 3. If Q (so YO(DO),,R"), thesilane of formula (II), in which E represents a halogenatom or an acyloxy radical, is reactedcompletely with the hydroxycompound of formula (III). The reaction is preferably completed byintroducing a nitrogen-containing base into the mixture which haspreviously been diluted with an inert solvent.

This technique is particularly useful if the oxime u HON-:

is of very low reactivity and hence has difficulty in reacting with thehalogen atoms or the acyloxy radicals. However, the compounds of formulaI obtained by this particular variant of the process are in the form ofmore complex mixtures than those-prepared by using either of two methodsfirst mentioned. These mixtures are ratherdifficult to separate byfractional distillation into pure silanes of formula (I) in which a l or2.

The starting silane of formula (ll),

can be obtained by partial reaction of a compound RSiE inwhich Erepresents a halogen atom or an acyloxy radical, with an oxime n HON=CThe silanes of formula I can be used in numerous fields of organosiliconchemistry and organic chemistry. For example, they can be substitutedfor the conventional cross-linking agents employed in organosiliconcompositions .which can be cured to give elastomers at ambienttemperature (that is to say within the range of l0 to +60 C.) in thepresence of water and are storage-stable in the absence of water. Theelastomers are those based .on polydiorgano-siloxanes terminated, ateach end of their chain, by a reactive radical such as hydroxyl, alkoxy,amino,-aminoxy, I

iminoxy or acyloxy group and there may also be incorporated in thecompositions customary fillers and a 8 ysilanes,epoxyalkoxyalkyltrialkoxysilanes, epoxycycloalkyltrialkoxysilanes andacroyloxyand methacroyloxy-alkyltrialkoxysilanes, to the most diversesubstrates to cause organosilicon derivatives and organic derivatives,such as resins, elastomers, varnishes, adhesives, undercoats and paints,to adhere to them. Finally, the silanes containing a radical R of thealkenyl, cycloalkenyl and ethynyl type can be copolymerized withorganosilicon monomers and polymers and with organic monomers andpolymers which themselves contain aliphatically unsaturated bonds, inthe presence of free radical generating reagents, so as together to forma combination of polymers with remarkable properties which can be usedin advanced fields of industry such as the continuous lacquering ofmetal panels and the coating of articles of complicated shapes by thefluidized bed technique; in this latter case, the polymers arepulverulent solids.

. The examples which follow illustrate the invention.

EXAMPLE 1 152 g: (0.66 mol) of a silane of formula CH Si(OCl-I CH OCH CIand 500 cm of anhydrous cyclohexane are introduced into a l l. flask,equipped with a reflux condenser, a stirrer, a dropping funnel, a gasinlet tube dipping to the bottom of the flask and a thermometer sleeve.

Anhydrous ammonia is introduced, by means of the gas inlet tube, intothis stirred solution, which is kept throughout the process at atemperature of about 35 C. by means of a waterbath placed under theflask. As soon as ammonia is introduced, a white precipitate. ofammonium chloride forms; the passage of ammonia lasts for about 1 hour10 minutes and is stopped when the ammonia has totally reacted with thereaction mixture and hence escapes from the flask.

Thereafter, 62 g. (1.05 mol) of acetaldehyde oxime are added to themixture over the course of 5 minutes, followed by 76 g. (0.3 mol) of thesilane already used, of formula CH Si(OCl-I Cl-l OCl-l Cl, added overthe course of 40 minutes. During this addition the temperature in thereaction mixture is throughout kept at about 35 C. by external cooling.

The mixture in the flask is then filtered, and the precipitate is washedwith 150 cm of cyclohexane; this wash solvent is added to the filtrateand the cyclohex' ane and the volatile products are removed by gradualheating under reduced pressure so as to reach a temperature of C. in themass and a pressure of 30 mm. of mercury. 230 g. of a colorless liquidof viscosity 3.2 centistokes (cSt) at 20 C. are obtained, which whenpurified by distillation yield a silane of average formula boiling at82- 87C. under 0.5-0.7 mm. of mercury, m, 1.429, d 1.045, the structureof which is confirmed by infra-red spectrophotometry.

The starting silane CH Si(OCl-I CH OCH Cl was prepared as follows. 897g. (6 mols) of methyltrichlorosilaneare introduced into a 2 l. flaskequipped with a reflux condenser, a stirrer, a dropping funnel, a gasinlet tube dipping to the bottom of the flask and a thermometer sleeve.When the stirrer is running, 684 g. (9 mols) of the monomethyl ether ofethylene glycol are added to this silane by means of the dropping fun-Boiling point of chlorine 1420 and 589 g. of the silane of formula: CHSi(OCH CH OCl-l Cl, having the following characteristics:

Boiling point 110-1 l 1C. of chlorine 15.75 d, 1.088 n 1.421

EXAMPLE 2 126 g. (0.66 mol) of the silane prepared in Example 1, offormula CH Si(OCH CH OCl-l )Cl and 500 cm of cyclohexane are introducedinto a l l. flask equipped as described in Example 1. Ammonia is thenintroduced into the stirred mixture, in sufficient amount to reactcompletely with the silane. During this addition, which lasts about 2hours, the temperature of the mixture does not exceed 30-35 C., becauseof external cooling.

The following are then successively added to this mixture, with constantstirring: 124 g. -(2.1 mols) of acetaldehyde oxime, over the course of 5minutes, followed by a solution of 63 g. (0.33 mol) of the silanealready used, of formula CH Si(OCH CH OCH )Cl in 50 cm of cyclohexane,added over the course of 1 hour, while constantly maintaining thetemperature of the reaction mixture at about 30-3 5 C.

The mixture is then filtered, the precipitate is washed with 150 cm ofcyclohexane, the washings being added to the filtrate, and the solventand the volatile products are removed by heating under reduced pressure.The residue of viscosity 5.35 cSt at 20 C., weighs 219 g. Ondistillation of this residue, the silane of formula CH SKOCH CH OCH(ON=CHCH boiling at 80 C. under 0.25 mm. of mercury, is recovered:

EXAMPLE 3 440 g. (2 mols) of liquid methyltriacetoxysilane, heated to atemperature of about 45 C., are added to a 2 l. flask equipped asdescribed in Example 1. The mixture is stirred, and 152 g. (2 mols) ofthe monomethyl ether of ethylene glycol are added to this silane overthe course of minutes, and stirring is then continued for about 30minutes; during this period of time the temperature of the reactionmixture drops slowly to ambient temperature. The acetic acid formed andthe volatile products are then removed by gradual heating under reducedpressure so as to reach a temperature in the mass of C. and a pressureof 15 mm. of mercury. 124 g. of acetic acid and of volatile products arethus collected.

245 g. (4.15 mols) of acetaldehyde oxime are added to the well-stirredresidue over the course of 20 minutes; the temperature rises a littleand does not exceed 30 C. Thereafter 600 cm of cyclohexane are added todilute the whole, and ammonia is immediately introduced into the mixtureto facilitate completing the reaction, the temperature being maintainedat about 30 C. by external cooling.

When the ammonia is evolved from the flask, its introduction is stopped,the precipitate is filtered and washed with 500 cm of cyclohexane whichare added to the filtrate, the solvent and the volatile products areremoved, and 457 g. of a colorless liquid residue of viscosity 5.2 cStat 20 C. are collected. This residue is purified by distillation, and asilane of average formula:

at 90 C. under 0.9-1 mm. of mercury is obtained, the structure of whichis determined with the aid of infrared absorption spectrophotometry.

EXAMPLE 4 440 g. (2 mols) of methyltriacetoxysilane heated to atemperature of 45 C. are introduced into a 2 l. flask equipped asdescribed in Example 1, the stirrer is started and 304 g. (4 mols) ofthe monomethyl ether of ethylene glycol are added over the course of 17minutes; stirring is then continued for 30 minutes. 241 g. of aceticacid and of volatile products are then removed by heating under reducedpressure and g. (2.2 mols) of acetaldehyde oxime are then added to theresidue over the course of 7 minutes.

The resulting mixture is diluted with 320 cm of cyclohexane and ammoniais introduced in the same manner as in Example 3 so as to complete thereaction, the temperature of the mixture being maintained at about 30 C.by external cooling. 496 g. of a liquid residue of viscosity 3.1 cSt at20 C. are obtained by treatment of the mixture similar to the treatmentof that of the preceding Example. This residue is purified bydistillation to give a silane of formula: CH Si(OCH CH OCH ON=CHCH b.p.0.3 about 80-81 C.; its formula is established by means of infra-redabsorption spectrophotometry.

EXAMPLE 5 A similar procedure to that of Examples 3 and 4 is followed byintroducing 440 g. (2 moles) of methyltriacetoxysilane into a 2 l. flaskequipped as already indicated, and adding 456 g. (6 mols) of themonomethyl ether of ethylene glycol over the course of 25 minutes.Stirring is continued for 30 minutes, and 367 g. of acetic acid and ofvolatile products are then removed by heating under reduced pressure. 34g. (0.58 mol) of acetaldehyde oxime are added to the residue over thecourse of 3 minutes, the mixture is diluted with 80 cm of cyclohexane,and ammonia is passed into the mixture to facilitate completion of thereaction. After working up as described in the previous Examples, 527 g.of a limpid residue of viscosity 2.4 cSt at 20 C. are collected, andthis material on distillation yields a silane of average formula:

boiling at 909 1 C. under 0.6 mm. of mercury.

EXAMPLE 6 cyclohexane, the solvent is removed and 1,777 'g. of a residueare collected and purified by distillation, yielding a silane of averageformula CH Si(ON=CH- CH (ocfl cn ocl-m having the followingcharacteristics:

Boiling point 93-'-94C.

Its structure is established by analysis with the aid of nuclearmagnetic resonance and infra-red absorption spectrophotometry.

EXAMPLE 7 On working under the same conditions as in Examples l and 2but replacing the methyltrichlorosilane by vinyltrichlorosilane, silanesare obtained of which the physical characteristics are set out in Table1.

TABLE I Density, i d e it f Physical characteristics Boiling point (1411 Silanes synthesised:

CH=CHS1C1;(0CHCH2OCH:) B.P.1a=66 C 1. 151 1.435

CH;=CHSiCl(OCH CH- OCH3)2 B.P.a-a=107109 C-. 1.091 1. 433 (ON=CHCHa)z B.P.zz =120-130 C 1. 056 1. 449

C Hz=G H Si O CHzCH2OCH3 ON='OH-OH B.P.u.s=99100 O 1. 04 1.437

C 11 :0 H Si (O CH2CH2O CHa)2 monomethyl ether of ethylene glycol areadded to the residue over the course of 7 minutes. As in the precedingExamples, the mixture is diluted with cyclohexane (900 cm and ammonia ispassed in for 5 hours to facilitate completion of the reaction. Duringthis period of time thetemperature is kept at about 40 C.

The mixture is filtered, the precipitate is washed with EXAMPLE 8Examples 1 and 2 are repeated, substituting phenyl- 40 trichlorosilanefor methyltrichlorosilane and using, in

addition to acetaldehyde oxime, butyraldehyde oxime; the silanes soprepared have the physical characteristics set out in Table 11.

OCHzCHzOCHIl EXAMPLE 9 Examples 1 and 2 are repeated, replacing themonomethyl ether of ethylene glycol by ethanol, n-butanol andisopropanol, and in addition to acetaldehyde oxime, using acetone oxime;the silanes synthesized have their physical characteristics set out inTable Ill.

EXAMPLE 10 Examples 1 and 2 are repeated, except that the monomethylether of ethylene glycol is replaced by the corresponding monoethylether; the physical characteristics of the silanes prepared are set outin Table IV.

TABLE III Refractive Density, index, Physical characteristics Boilingpoint d4 110 Silanes synthesized:

CHr-Si B.P.m=99101 C 1.100 1.398

O O H C Ha- S i H B,P.;-a=7080 C 1.005 1.428 O N=C\ C 1'13 S i CH3B.P.o.s=6775 C..... 0.987 1.435 0N=C\ CHzSi B P.o5=85 C 1. 0458 1. 4076CH3-S1 (ON=0H-CH )z OCH(CH3)2 B.P.1ru=114116 C 1. 0732 1. 3994 OH Si\/OC-H(CH 0.988 1.431 GHQ-Si (O N=CHCH3)2 OHaSi reacted with the oximesof acetone, methyl ethyl ketone and butyraldehyde, in accordance withthe above. The following mechanical properties are then measured on thefilms of silicone elastomer thus obtained, which are however left in airat about 20 C for one week to complete their crosslinking:

procedure described in Examples 1 and 2; the iminox- 5 Shore A hardness(Standard ASTM D 676-59 yalkylsilanes synthesized have their physicalcharac- Tensile Strength: RR (Standard AFNOR T teristics set out inTable V. H dumb-bells) TABLE v Dnnslty. Refractive Physicalcharacteristics Boiling point 11 index, 11.3"

Sllanes synthesised:

(OClI GlhOCllfl- 11.1.o.1.t.l=u3 o.-. v 1. 0211 1.430

crnsi ON=C(CH2)2 /CHCH;OCH;1 B.P. =92-94 0--.. 1 1.034 1.442 cmsi(ON=C(CH:)2)2

/(0CH CH OCHa)z BvP. =9799 c r. 1.015 1.431 CH3Si\ CH3 oN=o O CHzCHzOCH3 B.P.n,7=102107 C"..- 1. 000 1. 440

CHaSi /CH3 ON=C O CH2GH2O CH3 B..Po.1=106107 C 0. 998 1. 437

onlsi /H EXAMPLE 12 Elongation at break: A in (Standard AFNORT Anorganopolysiloxane composition is prepared by l g ms at Sh wn inintimately, mixing the following constituents, with ex- T bl s 0 esemeasureme e o clusion of moisture; 40 a e TABLE VIa,w:dihydroxydimethylpolysiloxane oil of v1scos1ty 20,000 cPo at 25C.100 g. Sample Sh,re A Tensnc elonsa, pyrogenic silica of specificsurface area 200 hardness Strength ion 8 m2] in kg/cm break finelyd1v1ded calcium carbonate 25 g. iminoxyorganoxysilane synthesized asdescribed in Example 2, of formula Fraction C 33 1&8 33o Fraction D 3116.5 300 OCHgCHzOCH:

cHlsi CH CH3) The remamder of the compos1t1on 1s packaged 1n a leakproofalummum tube. After 6 months storage the r appearance of the compositionremains unchanged and t I t d d b f db H 4 the elastic films which ityields on exposure to moisture ca a yS ertve [83C 1011 O l U! 1n edilauraw with biylonhmmanateyimhe show mechamcal propertlessubstantially comparable weight ratio of 100:27 by heating to 120 C. tothose shown in Table VI. Th1s type of compos1t1on 1s rm 3 I l used forthe manufacture of non-stick coatings and profractlon C this composlflonP f Over a tective coatings on metals, timber, paper, fabrics of inglassPiate prevlously coated Wllh a non-suck agemorganic or organic fibers,ceramic, earthenware and The layer fleposlted, of about 2 l lhlcklfssr15 P brick, as well as for caulking boats and encasing elecposed to airfor 24 hours, the relat1ve hum1d1ty being tronic equipment greater than50 percent and the temperature being of the order of 20 C: At the end ofthis period of time the EXAMPLE l3 layer has been converted into arubbery, firm and A composition is prepared by mixing the followingsupplyfilm which can easily be detached from the subingredients in ananhydrous atmosphere:

strate.

Another fraction D is subjected to accelerated aging by heating in aclosed flask for 96 hours at 100 C., and is then caused to cure on aglass plate as described u,ww-dihydroxydimethylpolysiloxane oil ofviscosity 80,000 cPo at 25C. I00 g. pyrogenic silica of specific surfacearea 200 m /g, treated with octamethylcyclotetrasiloxanc 20 g.

A fraction C and a fraction D, of this composition (the fraction D,being put aside to age by heating in a closed flask for 96 hours at 100C.) are spread on glass plates, in air at about 20 C., to yield rubberyfilms, in

accordance with the technique indicated in the precedl 5 ing Example.

The mechanical properties of the films are set out in Table VII.

The remainder of the composition is stored in a leakproof aluminum tube.After 6 months it is found that the stored composition has the samecapacity for cross- 30 linking in the presence of moisture as thatfreshly prepared. This type of composition is suitable for themanufacture of moulds which reproduce articles made of organic resins orof metals of low melting point, for

,taking dental impressions, for the production of supported orunsupported insulating tapes, and for gluing materials.

EXAMPLE 14 A crosslinking agent of the iminoxyorganoxysilane type,chosen from among those described in Examples 2, 7, 8, 9 and l l, ofwhich the formula and the amount employed are given in Table VIII, isincorporated in a composition consisting of:

a,w-dihydroxydimethylpolysiloxane oil of viscosity 300,000 cPo at 25C.[00 g. a,w-bis(trimethylsiloxy)dimethyl-polysiloxane oil of viscosity 20cPo at 25C. 100 g.

pyrogenic silica of specific surface area 200 mlg, treated withoctamethylcyclotetrasiloxane 27 g. catalyst used in Examples l2 and [30.2 g.

The compositions so prepared, which can be cured by atmospherichumidity, are used to obtain films of silicone elastomer by followingthe working method of Example 12; a fraction C of the compositions isemployed as such, and another fraction D is aged by heating in a closedflask for 96 hours at 100 C., and the remainder is stored with exclusionof moisture.

The mechanical properties of the films are set out in Table VIII; inaddition to the Shore A hardness, the tensile strength and theelongation at break, the modulus" is also given, that is to say the loadin kg/cm for an elongation of 100 percent (Standard AFNOR T 46,002, 11;;dumb-bells).

TABLE VIII Weight Type of Tensile Percent 833%? 522; ShoreA ill 5%;llfsfid Crosslinking agent in g. used hardness kgJcm. break kg./cm. 2

OCHzCH2OCHa C2 16 18.7 720 2. 3

CHaSi 3. 5

(ON=CHCH3)2 D2 15 12 635 1.9

OCH CH OClIa C2 18 18.7 710 2.3

C HsSi 4. 65

(ON=CHC I1 D 17 15.7 010 2 (ON=C (C1102); D2 15 13. 5 730 2. 1

CHaSi 4. 65

(ON=O (CHa)C;Ha)2 Dz 15 12 570 1.9

Ella Si 3. 76

(()N=C(C1I3)2): D 14 12.6 695 1.7

0 C HzCHzOCl'ls C1 16 21 875 1. 8 (31111581 '4. 74 1 (ON= (DH-CH3): D214 16 950 1. 5

OCHzCHgOCHa C2 15 19 3 840 2 2 CuHsSi 15. 61

(ON=CHC3H7): D2 l2 l2. 6 770 1. 6

O CHzCHzO CH3 CH2=CHS1 I3 94 C2 17 17 2 720 1 8 (ON=CHCHa)z 0 4 v C2 1819. 6 635 2. 7 CH3 S l6 (ON=QH-CHa)z D; 1s 1s. 5 560 2. 7

The compositions stored with the exclusion of moisture yield, onexposure to moisture after numerous months storage, silicone elastomerswhich display mechanical properties of the order of those mentioned inTable VIII.

These compositions, which become converted into elastomers of lowmodulus, are particularly useful for leakproof jointsuand expansionjoints in building, particularly for masonry, pavings, runways,pipelines, moulded articles and concrete constructions.

EXAMPLE A composition is prepared by intimately mixing the followingingredients with exclusion of air:

a,mdihydroxydimethylpolysiloxane oil of viscosity 18,400 cPo at C. I00g. pyrogenic silica of specific surface area 200 mlg 8 g.iminoxyorganoxysilane used in Example 12 of formula ON=OH-CH;) C s 7.5g.

0 CHQCHEO CHI catalyst used in Example 12 0.2 g.

On casting this composition on glass plates treated with a non-stickagent, supple, elastic and transparent films are obtained after exposureto air at about 20 C.

We claim;

1. A silane of the general formula wherein R represents an unsubstitutedmonovalent hydrocarbon radical, a halogen substituted monovalenthydrocarbon radical, an alkoxy substituted monovalent hydrocarbonradical ora nitrile substituted monovalent hydrocarbon radical, one of Yand Q represents a radical and the other of Y and Q represents a O(DO),,R" radical, and a represents a positive number in the range 0.1 to2.9 inclusive; the symbols R, which may be the same or different, eachrepresent a monovalent hydrocarbon radical, the symbols R, which may bethe same or different, each represent hydrogen or an alkyl radicalcontaining one to five carbon atoms or, together with R represent adivalent hydrocarbon radical, the symbols R, which may be the same ordifferent, each represent a monovalent aliphatic hydrocarbon radicalhaving one to four carbon atoms, the symbols D, which may be the same ordifferent, each represent an alkylene radical having one to eight carbonatoms and n=0, 1, 2 or 3.

2. A silane according to claim 1 wherein R represents an alkyl radicalhaving one to 12 carbon atoms or an alkenyl radical having two to 12carbon atoms.

3. A silane according to claim 1 wherein R represents a methyl, vinyl orphenyl radical.

4. The silane of claim 1 wherein R represent an alkyl group having oneto six carbon atoms.

5. The silane of claim 4 wherein R represents a methyl, ethyl or propylradical.

6. The silane of claim 1 wherein R" represents hydrogen or a methylradical.

7. The silane of claim 1 wherein D represents a CH CH radical.

8. The silane of claim 1 wherein R' represents a methyl, ethyl or propylradical.

9. The silane of claim 1 wherein R represents methyl, vinyl or phenyl, Rrepresents methyl, ethyl or propyl, R" represents hydrogen or methyl, Drepresents Cli Cl-l and R' represents methyl, ethyl or propyl.

10. A process for the preparation of a silane according to claim 1 whichcomprises completely reacting a compound of general formula:

wherein hal represents halogen, is reacted with ammonia or a primaryalkylamine or arylamine in an inert diluent, the resulting productreacted with an oxime of formula HO'N=CR'R and the resulting reactionproduct. reacted with the remaining one-third of the stoichiometricamount of the silane reactant.

13. A process according to claim 10 wherein a silane reactant offormula:

is reacted with an oxime of formula HON=CR'R", the mixture diluted withan inert diluent and ammonia or a primary alkylamine or arylamine addedto complete the reaction.

14. A process according to claim 10 wherein a silane reactant offormula:

is reacted with a hydroxy compound of formula:

2. A silane according to claim 1 wherein R represents an alkyl radicalhaving one to 12 carbon atoms or an alkenyl radical having two to 12carbon atoms.
 3. A silane according to claim 1 wherein R represents amethyl, vinyl or phenyl radical.
 4. The silane of claim 1 wherein R''represent an alkyl group having one to six carbon atoms.
 5. The silaneof claim 4 wherein R'' represents a methyl, ethyl or propyl radical. 6.The silane of claim 1 wherein R'''' represents hydrogen or a methylradical.
 7. The silane of claim 1 wherein D represents a-CH2CH2-radical.
 8. The silane of claim 1 wherein R'''''' represents amethyl, ethyl or propyl radical.
 9. The silane of claim 1 wherein Rrepresents methyl, vinyl or phenyl, R'' represents methyl, ethyl orpropyl, R'''' represents hydrogen or methyl, D represents -CH2CH2- andR'''''' represents methyl, ethyl or propyl.
 10. A process for thepreparation of a silane according to claim 1 which comprises completelyreacting a compound of general formula: with a compound of generalformula HY where E represents halogen or an acyloxy radical and R, Q, Yand a are as defined in claim
 11. A process according to claim 10wherein E represents chlorine or an acetoxy radical.
 12. A processaccording to claim 10 wherein about two-thirds of the stoichiometricamount of a silane reactant of formula: wherein hal represents halogen,is reacted with ammonia or a primary alkylamine or arylamine in an inertdiluent, the resulting product reacted with an oxime of formula HO.NCR''R'''' and the resulting reaction product reacted with The remainingone-third of the stoichiometric amount of the silane reactant.
 13. Aprocess according to claim 10 wherein a silane reactant of formula: isreacted with an oxime of formula HO.N CR''R'''', the mixture dilutedwith an inert diluent and ammonia or a primary alkylamine or arylamineadded to complete the reaction.
 14. A process according to claim 10wherein a silane reactant of formula: